Int. J. Electrochem. Sci.

, 6 (2011) 5016 - 5030

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

Corrosion of Carbon Steel in Sour Water From the Oil

Industry: the Effect of Temperature
E.M. Esparza Zúñiga1, M.A. Veloz Rodríguez1,*, J. Uruchurtu Chavarín2, V.E. Reyes Cruz1
1
Área Académica de Ciencias de la Tierra y Materiales. Universidad Autónoma del Estado de
Hidalgo. Carr. Pachuca Tulancingo Km 4.5, Col. Carboneras, Mineral de la Reforma, Hgo. México
2
Centro de Investigación en Ingeniería y Ciencias Aplicadas. Universidad Autónoma del Estado de
Morelos. Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Mor. México
*
E-mail: mveloz@uaeh.reduaeh.mx

Received: 5 August 2011 / Accepted: 11 September 2011 / Published: 1 October 2011

In this work, the corrosion behavior of carbon steel AISI 1018 immersed in a sour water sample
solution collected from a refinery plant, was studied, varying the temperature between 25 to 50°C with
and without stirring. Polarization curves indicate negligible modification of anodic branch without
stirring; but, the cathodic branch is more sensitive to temperature change. Also, analysis of surface
samples by scanning electron microscopy (SEM) shows no film of corrosion products. The values of
electrochemical noise localization index (LI), indicate that the sites of localized corrosion increase at
30°C. However, when solution is stirred, polarization curves indicate more sensibility in anodic branch
and SEM micrographs show different corrosion products. LI shows values approaching 1, indicating
sites where localized corrosion is present. These results indicate that the variation in temperature can
cause changes in the structure of the corrosion products and thus the severity of damage in the metal
surface.

Keywords: Corrosion, sour water, carbon steel, temperature

1. INTRODUCTION

Among the corrosion problems, one of the most important present in the refining oil industry, is
specifically the related to the sour water generated in primary distillation plants. Despite the efforts
made in the industrial field, and in fundamental studies; the different operating conditions as well as
different concentrations of pollutants, makes their control very complicated.
The studies that have been trying to simulate the operating conditions in sour waters [1-20]
have increased in the last ten years, in which the characteristics of the raw obtained, have changed
resulting in corrosive environments much more aggressive than before. The purpose of these studies
Int. J. Electrochem. Sci., Vol. 6, 2011 5017

was to try to find ways, in which various agents affect or minimize corrosion, with the purpose of
determining the predominant mechanism of corrosion in such environments.
On the other hand, carbon steel AISI 1018 is widely used as construction material in many
industries due to its excellent mechanical properties and low cost [21]. So, the evaluation of carbon
steel corrosion in H2S environments is very important in the petroleum industry, as this phenomenon is
responsible for costly social, economic and sometimes even human losses [20].
The sour water is considered as waste water containing sulfides and chlorides, among other
components; this kind of water is very harmful to metallic equipments that are in contact with it,
producing high corrosion rates leading to failures and material drainage and spilling [22].
An important factor involved in the process of corrosion, is the temperature, because the
corrosion rate increases as the temperature increase in the corrosion medium on the reactions
proceeding in pure acids [23]. However, this does not happen in all systems, for example, the steel
AISI 304 SS [24]; results indicated higher corrosion at high temperatures (more than 75 ºC), but at mid
temperatures (between 50 and 75 ºC) corrosion rates were similar; and at low or moderate
temperatures (between 25 and 50 ºC), the stainless steels are in true passive state below the transpasive
region. From early studies in the same work on the corrosion behaviour of AISI 304 using anodic
polarization method, it was observed, a smaller passive range at higher temperature and hence an
unstable passive film.
Finally, failures due to wet H2S cracking have been experienced extensively in production
operations, in refining and in pipelines. Many commonly used steels and alloys are susceptible to
cracking under the prevailing high temperatures, pressures and stresses [2]. On the other hand, many
places where the refining industries are located have drastic changes in atmospheric temperature
conditions and the damages in the equipment are severe.
The present study focuses in determining the corrosion effect on the carbon steel at different
temperatures when it is in the real corrosive medium. Here, the behaviour of carbon steel AISI 1018 at
temperatures between 25 and 50º C, is studied in the presence of a sour water sample from a primary
distillation plant of a Mexican Refinery. The studies were performed with and without stirring using a
rotating disk electrode to observe the flow effect, and trying to simulate operating conditions.

2. EXPERIMENTAL PART

Before collecting the samples of a sour water sample from a primary distillation plant of a
Mexican Refinery, a statistical study (not showed in this work) was performed where all the
parameters that change over a period of time, were identified. Afterwards, samples were collected from
a primary distillation plant of a Mexican Refinery using a sampling point of the dome in the distillation
tower. The composition ranges of the samples are showed in Table 1. Other studies are being
performed varying parameters like pH and chloride content, but they will be published later.
For the electrochemical study a typical three electrode cell setup was used with saturated
calomel electrode (S. C. E.) as reference and a graphite bar, as counter electrode. The working
electrode was AISI 1018 carbon steel disks with 0.5 or 0.7 cm2 of cross section area, embedded in a
Int. J. Electrochem. Sci., Vol. 6, 2011 5018

Teflon support. Prior to each experiment, electrode surface was polished with 600 SiC emery paper.
These electrodes were immersed in a sour water sample from the oil industry under 25, 30, 35, 40, 45
and 50 °C with and without stirring. The solution was deaerated with high purity nitrogen for 30 min
prior testing. When stirring, was used a 500 rpm rotating disk electrode during the tests. Nitrogen was
passed throughout the test, assuring de-oxygenating conditions as in the real operating conditions.

Table 1. Composition ranges for sour water samples from a Mexican primary plant refinery.

Component mg/l
3+
Al 0.01 - 0.11
Ba+2 0.02 - 0.12
Fe 2.41 - 2.87
+2
Mn 1.87 - 2.01
+
Na 19.23 - 22.31
Sulfide content as SO4- 62.31 - 64.32
+
NH4 2.78 - 3.47
+2
Ca 6.32 - 8.56
+2
Mg 2.96 - 3.46
K+ 4.36 - 6.88
+2
Sr 0.11 - 0.12
-
Cl 110 – 240
3+
Cr 0.03 - 0.22
pH range 6.63 - 7.33

Polarization curves were traced at a 0.1 mV/s scan rate, in a range of Ecorr ± 300 mV, following
a 10 minutes immersion of the electrode in the corrosive solution, time in which the corrosion potential
reached stability. Carbon steel AISI 1018 samples without exposure to corrosive medium, as well as
samples for each experiment polarized anodic and cathodically, were analyzed in the Scanning
Electron Microscope (SEM) and Energy Dispersive Spectrometer (EDS).
Electrochemical Noise measurements were performed using simple cells which consisted of
two ―identical‖ samples of AISI 1018 carbon steel and a SCE reference electrode, immersed in sour
water at the same temperature. Without stirring the samples have 0.5 cm2 area. When stirring, the
samples have 0.7 cm2 area and two ―identical‖ rotating disk electrodes at 500 rpm speed were used.
The solution was deaerated with high purity nitrogen for 30 min. 1024 measurements with a sampling
rate of 1 measurement per second was obtained. An ACM Gill AC and software for tests without
stirring, and with stirring conditions an Autolab PGSTAT 30 potentiostat—galvanostat and software
were employed. This was so, because the experiments were performed at two different laboratories,
previously observing reproducibility.
Int. J. Electrochem. Sci., Vol. 6, 2011 5019

3. RESULTS AND DISCUSSIONS

3.1 Temperature Without Stirring

In order to compare different temperatures, Fig. 1 shows polarization curves. At temperatures

of 25 to 40°C, anodic branches are very similar, but when the temperature increases at 45 and 50°C,
the current increased. Fig. 2 shows SEM images of surfaces at different temperatures of the anodic
scanned samples; it can be clearly seen the absence of corrosion products.

0.4
25 ºC 30 ºC
0.3 35 ºC 40 ºC
45 ºC 50 ºC
0.2
h = E-Ecorr (V)

0.1

-0.1

-0.2

-0.3

-0.4
-7 -6 -5 -4 -3
LOG I

Figure 1. Polarization curves obtained from AISI 1018 carbon steel in sour water at different
temperatures.

Figure 2. Surface resulting from the exposure of carbon steel AISI 1018 at temperature 40°C (a) and
50°C (b), on the electrode with anodic scan.
Int. J. Electrochem. Sci., Vol. 6, 2011 5020

Figure 3. Surface resulting from the exposure of carbon steel AISI 1018 at temperature 30°C (a) and
35°C (b), on the electrode with cathodic scan.

On the other hand, the cathodic branch is more sensitive to temperature change as it is observed
in Fig.1, at 25 to 40ºC, the reduction currents increased when temperature increased; while at high
temperatures, the current decreases and the slope increases in comparison with that at 35°C. However,
as in the anodic scan, the images of SEM in the cathodic scan (Fig. 3) showed clean surfaces, as
expected. Also the results of EDS at different temperatures did not show oxygen, which would indicate
the absence of corrosion products (oxides or hydroxides).
Table 2 shows the corrosion potentials (Ecorr), polarization resistances (Rp), Tafel slopes (ba and
bc; anodic and cathodic, respectively) and corrosion currents (Icorr) obtained from the polarization
curves at different temperatures; these calculations were made manually taking as a reference the
junction at the corrosion potential. The values of the corrosion potential are more negative than in
25°C, indicating that the reduction reaction is favoured on the metal surface, with the increase of
temperature. The cathodic slopes have higher values than the anodic ones, indicating the presence of
diffusive mass transport processes, possibly related to hydrogen evolution. On the other hand, the
polarization resistances show higher values compared to systems in sour acid mediums reported in the
literature [25], indicating less active surfaces.

Table 2. Corrosion parameters obtained from polarization curves, for AISI 1018 carbon steel in sour
water at different temperatures.

Temperature Ecorr Icorr Rp ba bc

°C (V vs. ESC) (A/cm2) (cm2) (V/dec) (V/dec)
25 -0.6796 5.49E-06 2056 0.2174 -0.8456
30 -0.6679 8.99E-06 1256 0.2957 -1.0647
35 -0.6905 7.92E-06 1426 0.2728 -0.6306
40 -0.6686 1.03E-05 1095 0.3232 -0.6581
45 -0.6961 8.32E-06 1357 0.2734 -1.2438
50 -0.6985 7.25E-06 1557 0.2289 -1.1614
Int. J. Electrochem. Sci., Vol. 6, 2011 5021

The corrosion currents, calculated from the Rp values (as it is done sometimes in industrial
corrosion monitoring), show low variation among them, as the increase in temperature had no effect.
However, as mentioned before, the temperature effect is on the cathodic reaction, which is reflected in
the cathodic slope values. This could be an indication of slight damage related with the hydrogen
evolution reaction.

25 ºC 30 ºC 35 ºC
6.00E-06
40 ºC 45 ºC 50 ºC

5.00E-06

4.00E-06

3.00E-06

2.00E-06
I (A/cm2)

1.00E-06

0.00E+00

-1.00E-06

-2.00E-06

-3.00E-06

-4.00E-06
0 200 400 600 800 1000
t (s)

Figure 4. Current time records for AISI 1018 carbon steel in sour water at different temperatures.

-0.640
25 ºC 30 ºC 35 ºC

40 ºC 45 ºC 50 ºC

-0.660

-0.680
E (V)

-0.700

-0.720

-0.740
0 200 400 600 800 1000
t (s)

Figure 5. Potential time records for AISI 1018 carbon steel in sour water at different temperatures.
Int. J. Electrochem. Sci., Vol. 6, 2011 5022

The experimental results obtained for carbon steel AISI 1018 in sour water conditions at
different temperatures without stirring, with sequential collection of potential and current noise data
are displayed in Figs. 4 and 5. Figure 4 shows experimental current noise data. For the 35°C
temperature condition and above, after transient behaviour dies out reaching steady state conditions,
some higher frequency and amplitude oscillations or higher noise level were observed, and therefore
more sites of localized corrosion. Although at 25 and 30 ºC, measurements suggest generalized
corrosion conditions, with no visible oscillations.
Figure 5 shows a slow fall in the potential at temperatures of 25, 35 and 40ºC, towards cathodic
potentials, associated with the active region; and then reaching the stationary state. At 30ºC
temperature, it increases toward anodic potentials. However, at 35, 45 and 50°C (Figs. 4 and 5), data
show steadily increase in current, which then falls rapidly, with little detectable current and potential
decay. As with noise current (Fig.4), some higher frequency and amplitude oscillations or higher noise
level were observed. Then the potential consists of the response of the passive surface (that must
provide the cathodic current) to the anodic current produced by pits; although these periods are much
less predictable in both amplitude and in time of occurrence than for carbon steel with 0.025M NaCl
[26].

Table 3. Corrosion parameters obtained from electrochemical noise, for AISI 1018 carbon steel
submerged in sour water at different temperatures.

Temperature  of I  of P Rn LI
ºC (A) (V) (cm²)
25 8.34E-08 7.54E-04 6442 0.0475
30 2.63E-07 3.15E-03 8527 0.4824
35 2.63E-07 2.95E-03 8005 0.1550
40 3.45E-07 4.73E-03 9762 0.1964
45 9.89E-08 2.27E-03 16345 0.1439
50 2.31E-07 1.75E-03 5412 0.1199

The noise resistance as a function of time is presented in Fig. 6, with average noise resistance
in the 100-1000 ohm-cm2 with some transients up to 10 000 ohm-cm2 observed, for the 30-40°C
temperature conditions. A local noise in the range 500-1024 seconds, were obtained with the results of
electrochemical noise parameters, presented in Table 3. The standard deviation of the current and
potential, the noise resistance (Rn) which is the standard deviation of the potential between the
standard deviation of the current ( Rn =  v /  i ), and the localization index (IL), obtained from the ratio
of the current standard deviation over the root mean square (rms) [27]:

IL =  i / irms (1)

1 n 2
rms =  ( xi )
n t =1
(2)
Int. J. Electrochem. Sci., Vol. 6, 2011 5023

10000000

25 ºC 30 ºC
35 ºC 40 ºC
1000000 45 ºC 50 ºC
LOG Rn (*cm2)

100000

10000

1000

100
0 200 400 600 800 1000
t (s)

Figure 6. Resistance time records for AISI 1018 carbon steel in sour water at different temperatures.

Table 3 shows that LI increased at 30ºC, which is the highest value of IL obtained, this
suggests localized events taking place over the surface. But when temperature is increasing, IL
decreased indicating that the sites of localized corrosion would be lower. It must be due to the
solubility of the corrosion products. Although, LI values suggest some localized attack, their values
close to 0.1 approach the mixed corrosion attack condition (LI 0.01-0.1), more likely since no
corrosion products were observed (Table 3). Also, the standard deviation of the current is greater for
temperatures of 30, 35, 40 and 50°C, suggesting that the corrosion rate is higher than with other
temperatures with less standard deviation of the current.
The different Rn did not show a trend in their behaviour, obtaining the greatest resistance at
45ºC and the less at 50°C. Also at temperatures between 30 and 40ºC, there is an intermediate effect on
the corrosion resistance, which could indicate that the effect of temperature allows the formation and
re-dissolution of corrosion products as a result of the cathodic reaction, reflected in the overall
corrosion rate. This has been reported before in the literature [20, 26].

3.2 Effect of Temperature under Stirring

In order to compare different temperature effects when the solution was stirred, Fig. 7 shows
polarization curves. At temperatures of 25 to 40°C, anodic branches are very similar and these
processes are also observed without stirring; however, when the temperature increases at 45°C, the
currents increased, but at 50°C anodic currents decreased again considerably, registering the lowest
values.
Int. J. Electrochem. Sci., Vol. 6, 2011 5024

0.4

25 ºC 30 ºC
0.3
35 ºC 40 ºC

45 ºC 50 ºC
0.2

0.1
h = E-Ecorr (V)

-0.1

-0.2

-0.3

-0.4
-7 -6 -5 -4 -3
LOG I

Figure 7. Polarization curves obtained from AISI 1018 carbon steel in sour water at different
temperatures with stirring.

Figure 8. Surface resulting from the exposure of carbon steel AISI 1018 at temperature 25°C (a) , (b),
30°C (c), (d) and 50°C (e), (f), on the electrode with anodic scan.

SEM images of anodic scanned samples (Fig. 8) shows a compact layer with small areas of
cracked film and formation of new corrosion products, which may be responsible for the similarity of
Int. J. Electrochem. Sci., Vol. 6, 2011 5025

the anodic currents at 25 to 40°C. At 50ºC the image shows layers of porous corrosion products, which
probably are not electrically conductive and would lead to the anodic oxidation currents being lower
than for the rest of the other temperatures.

Figure 9. Surface resulting from the exposure of carbon steel AISI 1018 at temperature 25°C (a), (b),
35°C (c), (d) and 45°C (e), (f), on the electrodes with cathodic scan.

Figure 10. Surface resulting from the exposure of carbon steel AISI 1018 at temperature 30°C (a) and
(b), on the electrodes with cathodic scan.

On the other hand, the system shows that cathodic branch samples (Fig. 9), are not very
sensitive to temperature change between 25 and 40ºC and both 45 and 50 °C, because the reduction
Int. J. Electrochem. Sci., Vol. 6, 2011 5026

currents are very similar. Although, the currents of the latter are higher than the rest of the
temperatures; at 30ºC the lowest reduction currents were obtained. On the contrary, when the system is
not stirred, the cathodic branch is more sensitive to temperature change. This is indicative that the
medium evolution is taking place in the system. SEM images of the electrode with cathodic scanned
samples (Fig. 9) show the formation of protective corrosion products. However at 45 and 50°C, the
surface of the electrodes have less corrosion products, but at 30°C (Fig. 10) shows a porous corrosion
layer, which may be responsible for the lowest reduction current.
Also, the results of EDS on the surfaces of the electrodes tested at different temperatures with
stirring, show the presence of oxygen compounds, which indicates, that the only corrosion products
formed are oxides or hydroxides with different stoichiometry, because they show differences in
morphology.
Table 4 shows the corrosion potentials (Ecorr), polarization resistances (Rp), Tafel slopes (ba and
bc; anodic and cathodic, respectively) and corrosion currents (Icorr) obtained from the polarization
curves at different temperatures. The values of the corrosion potential show that any reaction is
favoured when the temperature increases; exception made at 45ºC, which is 60 mV more negative.
This is observed in the anodic and cathodic slopes, because the values are similar between them,
though distant from the typical Tafel values, indicating that the system is controlled by mass transfer.
On the other hand, the polarization resistances show higher values with respect to the systems in sour
acid media reported in the in literature [25], but similar to the system without stirring (Table 2);
indicating the presence of slightly protective corrosion products or porous films. Also, the system at
50°C, has the greatest polarization resistance, although at 45°C, the lowest Rp was registered, which
may be related to the morphology of the corrosion products (see Figs. 8 and 9).

Table 4. Corrosion parameters obtained from polarization curves, for AISI 1018 carbon steel in sour
water at different temperatures, with stirring.

Temperature Ecorr Icorr Rp ba bc

°C (V vs. ESC) (A/cm2) (cm2) (V/dec) (V/dec)
25 -0.5960 1.99E-05 873 0.4160 -0.4696
30 -0.5826 1.98E-05 879 0.3638 -0.5045
35 -0.6015 2.00E-05 871 0.4343 -0.5876
40 -0.5902 1.50E-05 1161 0.4037 -0.4516
45 -0.6850 2.13E-05 817 0.3994 -0.4829
50 -0.6213 1.29E-05 1345 0.5117 -0.3484

The values of corrosion currents, which are directly related to the corrosion rate, are in the
same order of magnitude for all temperatures tested, indicating that apparently, the increase in
temperature has no effect. It shows that the corrosion rate calculated with Rp values cannot be a
reliable parameter, because the changes in both anodic and cathodic slopes and the morphology of the
corrosion products is different, as mentioned above.
Int. J. Electrochem. Sci., Vol. 6, 2011 5027

7.00E-09

2.00E-09

-3.00E-09
I (A/cm2)

-8.00E-09
25 ºC 30 ºC
35 ºC 40 ºC
45 ºC 50 ºC

-1.30E-08

-1.80E-08
0 200 400 600 800 1000
t (s)

Figure 11. Current time records for AISI 1018 carbon steel in sour water at different temperatures with
stirring.

-0.560
25 ºC 30 ºC
35 ºC 40 ºC
45 ºC 50 ºC
-0.590

-0.620

-0.650
E (V)

-0.680

-0.710

-0.740
0 200 400 600 800 1000
t (s)

Figure 12. Potential time records for AISI 1018 carbon steel in sour water at different temperatures
with stirring.
Int. J. Electrochem. Sci., Vol. 6, 2011 5028

Figs. 11 and 12 show the sequential collection of potential and current noise data, showing
current noise data (Fig.11) at 25 and 30ºC temperatures, presenting random behaviour or white noise,
reaching these oscillations amplitudes around (-5X10-9 to 5X10-9 A/cm2), but for another temperatures
these oscillations are of lower amplitude (-2X10-9 to 2X10-9 A/cm2). So, the first temperatures have
increased levels of noise, but in systems without stirring the solution, there are smaller amplitudes
registered. Thus stirring the solution, results in a greater increase in the noise amplitude. This is
presumably as a result of enhanced mass transport, as in 304 SS [28].
Figure 12 shows some initial transient behaviour reaching stability. All measurements did not
present oscillations, except for the initial transient. A slow fall in potential at 25, 30 and 40ºC, toward
more cathodic potentials associated with the active region. However, at 35, 45 and 50ºC, the potential
rose anodically, while at 40, 45 and 50°C reached the steady state. Also, these effects are present in
systems without stirring (Fig. 5), but at different potential values, because when stirring the potential
increase becomes more anodic.
A local analysis of noise data on the 500 to 1024 seconds range, were obtained with the results
of electrochemical noise showed in Table 5. Table 5 shows that the LI is similar for all temperatures,
and its value is close to 1.0, which suggests that the different samples at different temperature
conditions, present localized attack. So, the standard deviation of the current is greater at 25, 30 and
50ºC, implying that the corrosion rate is higher than in other temperatures, which have lower standard
deviation of the current.

Table 5. Corrosion parameters obtained from electrochemical noise, for AISI 1018 carbon steel
submerged in sour water at different temperatures with stirring.

Temperature  of I  of P Rn LI
ºC (A) (V) (kcm²)
25 6.44E-10 6.06E-03 6700 0.9996
30 7.53E-10 9.49E-03 8977 0.99997
35 3.98E-10 4.06E-03 7276 0.9978
40 4.59E-10 3.54E-03 5499 0.9991
45 2.85E-10 1.88E-03 4706 0.9982
50 8.16E-10 3.45E-03 3018 0.9992

As well as without stirring Rn, did not present any trend for the different temperature
conditions because the greatest resistance is at 30ºC, and less at 50°C (Fig. 13). For other temperatures,
there is an intermediate and variable effect on the corrosion resistance. These could indicate that the
effect of temperature allows the formation and redissolution of corrosion products as a result of the
cathodic reaction.
Int. J. Electrochem. Sci., Vol. 6, 2011 5029

1.00E+12 25 ºC 30 ºC
35 ºC 40 ºC
45 ºC 50 ºC

1.00E+11

1.00E+10
LOG Rn (*cm2)

1.00E+09

1.00E+08

1.00E+07
0 200 400 600 800 1000
t (s)

Figure 13. Resistance time records for AISI 1018 carbon steel in sour water at different temperatures
with stirring.

4. CONCLUSIONS

The system under study at different temperatures without stirring did not show the presence of
corrosion products and the temperatures where changes in behaviour were observed are at 30 and
45ºC.
On the other hand stirring the solution, shows results indicating that the variation in operating
temperature can cause changes in the structure of the corrosion products and therefore the damage in
the exposed material, even when the corrosion rate obtained through Rp did not show any differences.
Also, the temperatures where changes in behaviour where observed were at 30 and 50ºC. This implies
that equipment submitted to extreme temperature changes could be affected in an irreversible way,
because of the corrosion products formed and the possibility of localized corrosion. For this reason it is
very important the strict control of the operating temperature in all the pipelines and equipment where
the sour water contents are present.

ACKNOWLEDGEMENTS
The authors acknowledge the financial aid received from SEP-CONACyT (project No. 023889) and
PROMEP (project UAEHGO-PTC-293). E. Esparza express her gratitude to CONACyT and
ECOES—Santander for their economic support.
Int. J. Electrochem. Sci., Vol. 6, 2011 5030

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